Thermodynamics-antioxidant activity relationships of some 4-benzylidenamino-4, 5-dihydro-1h-1,2,4-triazol-5-one derivatives: Theoretical evaluation

Figures & data

Figure 1. Numbering system used to designate specific atom of the 4-benzylidenamino-4, 5-dihydro-1H-1, 2, 4-triazol-5-ones. A and specification of electron donating or withdrawing substituent used.

Figure 2. Structure of 1-acetyl-4-(p-chlorobenzylideneamino)-3-methyl-4, 5-dihydro-1H-1, 2, 4-triazol-5-one used for geometrical comparison.

Table 1. Relevant B3LYP/6-31G(d,p) geometrical parameters of BDHTD in various media.

	GAS					WATER					BENZENE
	Bond lengths				Bond angles	Bond lengths				Bond angles	Bond lengths				Bond angles
	N1-N2	C2=N3	C3-C5	H2…O1	O2 H2…H1	N1-N2	C2=N3	C3-C5	H2…O1	O2 H2…H1	N1-N2	C2=N3	C3-C5	H2…O1	O2 H2…H1
A	1.411	1.290	1.466	2.115	114.4	1.402	1.293	1.462	2.108	114.0	1.399	1.292	1.462	2.108	114.3
B	1.410	1.289	1.467	2.114	114.4	1.401	1.293	1.462	2.110	114.0	1.412	1.2901	1.466	2.115	114.2
C	1.409	1.289	1.466	2.114	114.4	1.401	1.293	1.462	2.112	113.9	1.398	1.292	1.463	2.109	114.3
D	1.396	1.291	1.463	2.110	114.6	1.402	1.293	1.462	2.112	113.9	1.399	1.292	1.462	2.110	114.2
E	1.409	1.289	1.467	2.114	114.4	1.405	1.293	1.461	2.109	113.9	1.401	1.293	1.462	2.108	114.2
F	1.408	1.289	1.467	2.114	114.5	1.401	1.293	1.462	2.111	113.9	1.398	1.292	1.462	2.111	114.2
G	1.417	1.289	1.465	2.114	114.3	1.406	1.294	1.460	2.108	113.9	1.417	1.290	1.463	2.113	114.1
H	1.399	1.291	1.461	2.109	114.4	1.404	1.294	1.460	2.110	113.9	1.401	1.293	1.461	2.110	114.1
I	1.399	1.291	1.462	2.110	114.4	1.403	1.294	1.460	2.109	113.9	1.401	1.292	1.461	2.109	114.2
J	1.406	1.291	1.464	2.112	114.5	1.399	1.293	1.462	2.110	114.0	1.405	1.292	1.463	2.112	114.2
K	1.416	1.288	1.467	2.115	114.5	1.404	1.291	1.462	2.111	113.9	1.416	1.289	1.466	2.114	114.2
L	1.412	1.290	1.465	2.113	114.3	1.406	1.294	1.460	2.109	113.9	1.403	1.293	1.461	2.109	114.1
M	1.406	1.290	1.463	2.110	114.4	1.409	1.292	1.461	2.110	113.9	1.408	1.291	1.462	2.109	114.1
Exp	1.378 ^[48]	1.271^[48]	1.447^[48]

Table 2. Relevant B3LYP/6-31G(d,p) geometrical parameters of BDHTD in various media.

Gas	BDE1	BDE2	BDE4	IP	PDE1	PDE2	PDE4	PA1	PA2	PA4	ETE1	ETE2	ETE4
A	312	351	380	705	924	962	991	1395	1422	1468	234	246	228
B	312	344	373	694	935	967	996	1400	1424	1478	229	237	212
C	312	344	374	691	937	969	999	1400	1424	1476	228	236	214
D	314	346	375	692	939	970	1000	1402	1426	1478	228	236	214
E	311	343	356	679	949	981	994	1397	1419	1445	231	241	228
F	311	342	354	672	956	987	998	1404	1426	1459	223	233	211
G	315	347	374	721	910	943	969	1392	1415	1450	240	249	240
H	316	349	375	718	914	947	973	1394	1416	1440	238	249	251
I	316	348	374	714	918	950	977	1395	1417	1440	237	248	251
J	312	343	344	673	956	986	988	1410	1429	1488	219	231	173
K	313	345	362	691	939	971	988	1403	1430	1475	227	232	203
L	313	345	378	718	912	944	977	1382	1404	1420	248	258	274
M	315	348	382	710	922	955	990	1394	1417	1423	238	271	276
	BDFE1	BDFE2	BDFE4	IPFE	PDFE1	PDFE2	PDFE4	PAFE1	PAFE2	PAFE4	ETFE1	ETFE2	ETFE4
A	279	315	345	697	893	929	958	1364	1388	1438	233	246	225
B	278	309	337	685	904	935	963	1369	1391	1448	227	236	208
C	279	310	337	683	907	938	965	1369	1392	1446	228	236	210
D	281	311	339	684	908	938	966	1371	1394	1448	228	236	209
E	276	306	321	670	917	948	962	1365	1385	1415	229	239	225
F	277	308	319	662	927	957	969	1371	1391	1430	224	235	207
G	281	313	339	714	878	910	936	1360	1382	1421	239	249	236
H	282	314	340	711	859	915	941	1362	1383	1411	238	250	248
I	283	314	340	708	886	918	943	1363	1382	1410	238	251	248
J	279	309	310	665	925	955	957	1379	1396	1458	219	231	171
K	280	311	326	683	908	940	955	1373	1397	1446	225	232	198
L	279	311	341	708	883	914	945	1352	1371	1391	245	258	268
M	282	314	347	703	890	923	955	1362	1383	1394	238	249	271

Table 3. B3LYP/6-31G(d,p) reaction thermodynamic energies in kJ/mol in gas-phase: reaction enthalpies and reaction free energies.

Benzene	BDE1	BDE2	BDE4	IP	PDE1	PDE2	PDE4	PA1	PA2	PA3	ETE1	ETE2	ETE4
A	317	343	380	608	116	142	179	409	427	465	315	323	322
B	314	339	370	598	123	148	179	406	425	470	314	320	306
C	317	342	374	599	124	150	181	411	429	475	312	320	305
D	317	343	373	599	124	150	180	410	429	472	313	320	308
E	316	342	359	595	128	153	170	409	428	452	314	321	314
F	317	342	354	587	136	162	174	412	431	462	311	318	298
G	316	343	372	618	104	131	160	400	418	445	322	331	333
H	319	346	375	618	107	134	163	403	421	439	322	331	342
I	319	345		616	109	135		404	422	439	321	330
J	314	338	339	575	145	170	170	412	428	479	308	317	266
K	314	340	324	597	124	149	133	408	428	468	313	318	263
L	319	346	381	621	104	131	166	399	417	427	327	336	360
M	319	345	383	620	105	132	169	401	423	424	324	329	365
	BDFE1	BDFE2	BDFE4	IPFE	PDFE1	PDFE2	PDFE4	PAFE1	PAFE2	PAFE4	ETFE1	ETFE2	ETFE4
A	284	309	346	546	-66	-42	-5	229	244	285	250	260	256
B	280	305	334	535	-60	-35	-6	225	243	291	250	257	239
C	286	310	340	537	-56	-32	-2	231	249	298	249	257	237
D	285	310	338	538	-57	-32	-5	232	250	299	249	256	234
E	284	308	326	533	-53	-29	-12	230	247	275	250	257	246
F	284	308	320	523	-43	-20	-8	234	248	285	246	255	230
G	283	309	338	556	-77	-52	-22	219	236	267	260	268	266
H	286	312	341	553	-72	-46	-17	223	240	259	258	267	276
I	285	312		555	-74	-48		224	239	260	256	268
J	283	306	306	514	-36	-13	-13	232	247	301	246	254	200
K	282	307	290	536	-59	-33	-50	225	248	292	252	255	193
L	284	309	343	557	-77	-53	-19	220	234	248	260	270	290
M	286	312	346	558	-77	-51	-17	229	243	246	252	264	295

^aUsed solvation enthalpies:^[23,43] = 6.4 kJ/mol, = 894 kJ/mol, = –7 kJ/mol.

Table 4. B3LYP/6-31G(d,p) reaction thermodynamic energies in kJ/mol in benzene^ab: reaction enthalpies and reaction free energies.

Water	BDE1	BDE2	BDE4	IP	PDE1	PDE2	PDE4	PA1	PA2	PA4	ETE1	ETE2	ETE4
A	329	338	379	443	66	76	116	205	218	245	304	301	314
B	322	338	370	439	63	79	112	206	219	253	296	300	298
C	322	338	371	438	64	80	113	206	219	254	296	299	298
D	322	338	371	438	64	80	113	206	219	253	296	299	298
E	320	336	357	439	61	77	98	203	216	236	297	300	302
F	322	338	351	428	74	90	103	206	216	245	296	302	286
G	324	341	374	452	52	69	103	203	215	232	301	307	323
H	324	341	374	451	53	70	103	203	214	225	302	308	330
I	324	341		450	53	71		203	214	225	301	307
J	321	337	335	408	94	110	107	207	219	259	295	299	256
K	322	339	357	442	61	77	95	206	219	253	297	300	284
L	324	341	380	451	53	70	109	203	214	215	301	307	345
M	304	341	382	452	32	69	111	203	215	212	281	306	351
	BDFE1	BDFE2	BDFE4	IPFE	PDFE1	PDFE2	PDFE4	PAFE1	PAFE2	PAFE4	ETFE1	ETFE2	ETFE4
A	296	304	344	392	-16	-8	32	125	135	165	251	249	259
B	288	304	335	387	-18	-2	29	126	135	172	243	249	244
C	289	305	336	387	-18	-2	28	126	138	173	243	247	243
D	288	305	336	388	-19	-3	29	125	137	173	243	248	243
E	289	305	324	389	-20	-4	15	126	138	158	243	247	246
F	289	304	318	376	-7	8	22	127	143	166	242	241	232
G	291	307	341	401	-30	-14	20	124	131	152	247	256	269
H	290	307	341	399	-29	-12	22	123	132	144	247	256	277
I	290	307		399	-29	-12		123	133	143	247	255
J	287	303	300	354	13	28	25	126	136	178	241	247	202
K	289	305	322	390	-20	-5	12	126	136	172	243	249	230
L	289	305	344	399	-30	-14	24	123	133	134	246	252	289
M	269	306	346	401	-52	-15	25	123	133	131	225	253	295

^aUsed solvation enthalpies:^[23,43] = –4 kJ/mol, = –1022 kJ/mol, = –105 kJ/mol.

^bUsed solvation free energy:^[47] = –27.7 kJ/mol, = –1104.5 kJ/mol, = –156.8 kJ/mol.

Figure 3. Thermodynamic energies of BDHTD (in kJ/mol) in gas phase for J molecule (R = NH₂) in water and benzene: BDE₁, IP, PDE₁, PA₁, and ETE₁.

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